EP1505668A2 - Method for manufacturing alkaline battery - Google Patents
Method for manufacturing alkaline battery Download PDFInfo
- Publication number
- EP1505668A2 EP1505668A2 EP04010472A EP04010472A EP1505668A2 EP 1505668 A2 EP1505668 A2 EP 1505668A2 EP 04010472 A EP04010472 A EP 04010472A EP 04010472 A EP04010472 A EP 04010472A EP 1505668 A2 EP1505668 A2 EP 1505668A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- negative electrode
- electrode cup
- mask
- cup
- alkaline battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 7
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000004544 sputter deposition Methods 0.000 claims description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- 239000011247 coating layer Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000005240 physical vapour deposition Methods 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- 238000007733 ion plating Methods 0.000 claims description 2
- 101150038956 cup-4 gene Proteins 0.000 abstract description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 210000000707 wrist Anatomy 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
- H01M10/283—Cells or batteries with two cup-shaped or cylindrical collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Definitions
- the present invention relates to a method suitable for use in manufacturing a coin-type or button-type alkaline battery used in small-sized electronic equipment such as an electronic wrist watch, an electronic desk calculator, or the like.
- numeral 1 denotes positive electrode mixture containing silver oxide or manganese dioxide as a positive active material, and in this example the positive electrode mixture 1 is formed into a pellet of a coin shape.
- the positive electrode mixture of the coin-shaped pellet is provided in a positive electrode can 2, which is composed of a nickel-plated stainless steel plate and functions as a positive electrode terminal and a positive electrode current collector.
- numeral 3 denotes negative electrode mixture in gel state without mercury, containing zinc or zinc alloy powder as a negative active material and composed of alkaline electrolyte such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, thickener, and the like; and the negative electrode mixture 3 is provided in a negative electrode cup 4 functioning as a negative electrode terminal and a negative electrode current collector.
- a separator 5 composed of a graft-polymerized three-layer film consisting of non woven fabric, cellophane, and polyethylene is provided. Then, the separator 5 is impregnated with alkaline electrolyte, for example, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
- a gasket 6 made of nylon is provided on the inner periphery of the positive electrode can 2 between the upper surface of the separator 5, and a cuff portion 4a and a cuff bottom portion 4b of the negative electrode cup 4; and the positive electrode can 2 is swaged and caulked to be hermetically sealed.
- the negative electrode cup 4 in this example is formed of a three-layer clad member made of nickel (Ni) 7, stainless 8, and copper (Cu) 9; and on the periphery thereof the cuff portion 4a and cuff bottom portion 4b are provided. Then, the inside surface area of copper 9 other than the cuff portion 4a and cuff bottom portion 4b is coated with stannum (Sn) having a higher hydrogen overpotential than copper to provide a stannum coating layer 10.
- stannum stannum
- Patent document 1 There has been known such an example of Patent document 1, in which only on the inside surface area of copper 9 other than the cuff portion 4a and cuff bottom portion 4b is coated with stannum (Sn) to provide the stannum coating layer 10.
- stannum Sn
- Patent document 1 the art relating to a coin type and button type alkaline battery is described in which the inside surface of the negative electrode cup 4 other than the cuff portion 4a and cuff bottom portion 4b thereof is coated with metal or metal alloy having a higher hydrogen overpotential than copper by means of a dry-type film forming method.
- H 2 hydrogen gas
- metal or metal alloy without using mercury having a higher hydrogen overpotential than copper is not deposited on the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4
- rising-up of the alkaline electrolyte creep phenomenon
- metal or metal alloy having a higher hydrogen overpotential than copper is deposited by means of a dry-type film forming method, the cuff portion 4a and cuff bottom portion 4b of the copper surface 9 are not oxidized, so that the liquid leakage resistance can be maintained against the creep phenomenon of the alkaline electrolyte.
- a circular counter-boring portion of 6 mm in diameter where the negative electrode cup 4 is mounted and fastened with a screw and a circular opening of 5 mm in diameter provided at the center of the counter-boring portion causing sputtering atoms to reach the inside of the negative electrode cup 4 are provided; and a negative electrode cup mounting portion 21C is formed on the negative electrode cup mounting side of the mask 21.
- the negative electrode cup 4 is set such that the negative electrode cup mounting portion 21C is covered by the negative electrode cup 4 put from the negative electrode cup supplying side (from the upper side in the figure), and then sputtering atoms are projected from the negative electrode cup mounting side (from the lower side in the figure) to be deposited.
- the mask is made of comparatively thin metal plate or the like and is shaped having the negative electrode cup mounting portion 21C as illustrated.
- the mask 21 is deformed by heat generated in sputtering or the like to cause position dispersion with respect to the negative electrode cup 4 mounted on the mask 21, so that the stannum coating layer 10 can not be favorably formed on the negative electrode cup 4, which results in inconvenience when mass production of the negative electrode cup 4 is conducted.
- the present invention provides a method for manufacturing an environmentally-benign alkaline battery without containing mercury (Hg), in which a mask used when PVD (physical vapor deposition) method of a dry-type film forming method is employed is appropriately shaped and the inconvenience at mass production of the negative electrode cup is improved.
- a method for manufacturing an alkaline battery according to the present invention is the manufacturing method of forming and processing a coating of a negative electrode cup by means of a PVD method such as deposition, sputtering, ion plating, and the like, in which the coating is performed using a mask with a mask opening in the shape that satisfies 2(2t+d)-B ⁇ A ⁇ 0.7d, where d is the inside diameter of a negative electrode cup, t is the thickness of the negative electrode cup, A is the diameter of the mask opening on the negative electrode cup mounting side, and B is the diameter of the mask opening on the negative electrode cup supplying side; and that satisfies (A/2)-h ⁇ C >0mm, where h is the depth of the negative electrode cup, and C is the thickness of the mask on the negative electrode cup mounting side, with a tapered angle D of the mask opening on the negative electrode cup mounting side being 90°>D ⁇ 45°.
- a PVD method such as deposition, sputtering, ion
- the mask in which, for example, the diameter of the mask opening on the negative electrode cup mounting side A is approximately 5mm, the depth from the negative electrode mounting surface 11d to the mask opening E is thickened into approximately 5mm, which is conventionally 0.2mm, and the tapered angle of the mask opening on the negative electrode cup mounting side is made to be 45°.
- the plate is made thicker and the taper is provided so that sputtering atoms are not blocked their paths by the mask, coating by means of sputtering is performed without damaging the uniformity thereof; and since the mask is made thicker, dispersion with respect to the position of the negative electrode cup caused by deformation of the mask due to heat or the like on sputtering and deformation of the mask caused when an excessive coating adhered to the mask is removed for cleaning is reduced, so that the operating life of the mask becomes longer and suitable for use in the mass production.
- FIG. 3 An example of the alkaline battery according to the embodiment of the present invention is shown in FIG. 3.
- numeral 1 denotes positive electrode mixture having silver oxide or manganese dioxide as a positive active material and in this example the positive electrode mixture 1 is formed into a pellet of a coin shape.
- the positive electrode mixture 1 in coin shape is provided in a positive electrode can 2 made of a stainless steel plate with nickel plating, functioning as a positive terminal and a positive current collector.
- numeral 3 denotes negative electrode mixture in a gel state that has zinc (Zn) or zinc alloy powder as a negative active material without containing mercury, formed of alkaline electrolyte such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, thickener, and the like; and the negative electrode mixture 3 is provided in a negative electrode cup 4 functioning as a negative electrode and a negative electrode current collector.
- a separator 5 composed of a three-layer film consisting of non woven fabric, cellophane, and polyethylene through graft polymerization is provided. Then, the separator 5 is impregnated with alkaline electrolyte, for example, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
- alkaline electrolyte for example, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
- a gasket 6 made of nylon is provided on the inside periphery of the positive electrode can 2 between the upper surface of the separator 5 and a cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4; and the positive electrode can 2 and negative electrode cup 4 are swaged and caulked to be hermetically sealed.
- the negative electrode cup 4 is formed of a three-layer clad material made of nickel 7, stainless 8, and copper 9; and on the periphery thereof the cuff portion 4a and cuff bottom portion 4b are provided.
- the inside surface area of copper 9 other than the cuff portion 4a and cuff bottom portion 4b is coated by sputtering that is one of PVD methods with stannum (Sn) having a higher hydrogen potential than copper to provide a stannum coating layer 10.
- a mask 11 hereupon used for partly forming a coating by sputtering is shown in FIG. 2.
- the mask 11 has the shape that satisfies the formula 2(2t+d)-B ⁇ A>0.7d , where A is the diameter of a mask opening on the negative electrode cup mounting side, B is the diameter of the mask opening on the negative electrode cup supplying side, d is the inside diameter of the negative electrode cup, and t is the thickness of the negative electrode cup.
- the cuff bottom portion 4b of the negative electrode cup 4 is not exposed to the inside of the mask opening on the negative electrode cup mounting side, so that only the inside surface area of the negative electrode cup 4 other than the cuff portion 4a and cuff bottom portion 4b is coated.
- the mask opening on the negative electrode cup mounting side has the shape, in which when h is the depth of the negative electrode cup, C is the thickness of the mask on the negative electrode cup mounting side, and D is a tapered angle of the mask opening on the negative electrode cup mounting side, the formula (A/2)-h ⁇ C>0mm is satisfied and the formula 90°>D ⁇ 45° is satisfied.
- the above described shape when sputtering atoms entering the outside portion from the center of the negative electrode cup 4 in the oblique direction at an angle of 45° or more is selected to be the reference dimensions, the sputtering atoms entering in the oblique direction are not blocked by the mask and the film thickness on the inside wall surface is not made thin. Accordingly, the thickness of the mask according to this embodiment is increased to provide a mask having the opening of dimensions suitable for the mass production.
- the coating layer is not formed on the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 and a copper surface of the gasket seal portion in which rising-up of alkaline electrolyte is less than the stannum coating layer 10 remains, and the copper surface 9 that is a base member of the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is not oxidized, so that liquid leakage resistance is secured.
- the mask 11 for partly forming a film is prepared, in which the thickness of the mask on the negative electrode cup mounting side is 0.2mm in FIG. 2.
- the negative electrode cup 4 is set on the mask 11 that covers the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 and sputtering is performed, so that the negative electrode cup 4 in which the coating layer 10 of approximately 0.01 ⁇ m made of stannum that is an example of metal having high hydrogen overpotential is provided on the inside surface area thereof.
- A/d is defined as a mask opening ratio
- an alkaline battery in button shape shown in FIG. 3 is manufactured using the above described negative electrode cup 4.
- alkaline electrolyte consisting of sodium hydroxide aqueous solution of 28% by weight is injected into the positive electrode can 2; then a pellet of coin shape formed of positive electrode mixture 1 containing silver oxide, manganese dioxide, and polyethylene tetrafluoride is inserted; and the alkaline electrolyte is impregnated into the positive electrode mixture.
- a separator 5 of a punched out circular shape having a three-layer structure made of graft-polymerized film formed of polyethylene and cellophane laminated and non woven fabric is set on the pellet of the positive electrode mixture 1; and the gasket 6 of nylon 66 coated with nylon 610 is set.
- alkaline electrolyte of sodium hydroxide aqueous solution of 28% by weight is dropped onto the non woven fabric of the separator 5 to be impregnated.
- the gel-state negative electrode mixture 3 composed of zinc alloy powder without mercury, containing aluminum (Al), indium (In), and bismuth (Bi); thickener; and sodium hydroxide aqueous solution is loaded; and then the negative electrode cup 4 is mounted on the negative electrode mixture 3.
- the positive electrode can 2 is swaged and caulked to manufacture an alkaline battery, for example, SR626SW in button shape and the alkaline battery of the practice example 1 is thus obtained.
- the above negative electrode cup 4 is used in an alkaline battery of the practice example 2, the other structure of which is similar to the practice example 1, to manufacture the alkaline battery of button shape, such as SR626SW.
- the above negative electrode cup 4 is used in an alkaline battery of the comparative example 1, the other structure of which is similar to the practice example 1, to manufacture the alkaline battery of button shape, such as SR626SW.
- the above negative electrode cup 4 is used in an alkaline battery of the comparative example 2, the other structure of which is similar to the practice example 1, to manufacture the alkaline battery of button shape, such as SR626SW.
- the negative electrode cup 4 of a comparative example 3 in Table 1 is subjected to sputtering similar to the comparative example 1 except that the mask is not used.
- the above negative electrode cup 4 is used in an alkaline battery of the comparative example 3, the other structure of which is similar to the practice example 1, to manufacture the alkaline battery of button shape, such as SR626SW.
- One hundred alkaline batteries for each of the above described practice examples 1, 2, and comparative examples 1 to 3 are prepared to be preserved in the environment of 45°C in temperature and at 93% relative humidity for one hundred days; and then a liquid leakage occurrence ratio is measured.
- the above negative electrode cup 4 is set on the mask 11 having the taper that covers the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4, in which by sputtering the inside surface area is coated with the stannum coating layer 10 having the thickness of 0.01 ⁇ m.
- the negative electrode cup 4 in the comparative example 4 uses the above mask, and similarly to the practice example 1 the inside surface area other than the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is provided by sputtering the stannum coating layer 10 of 0.01 ⁇ m in thickness.
- An alkaline battery of the comparative example 4 uses the above described negative electrode cup 4, and the other process similar to the practice example 1 is taken to manufacture the alkaline battery in button shape, for example, SR626SW.
- the negative electrode cup 4 in the comparative example 5 uses the above mask, and similarly to the practice example 1 the inside surface area other than the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is coated by sputtering with the stannum coating layer 10 of 0.01 ⁇ m in thickness.
- An alkaline battery of the comparative example 5 uses the above described negative electrode cup 4, and the other process similar to the practice example 1 is taken to manufacture the alkaline battery in button shape, for example, SR626SW.
- each of the alkaline batteries of practice example 3 and comparative example 4 where a negative electrode cup 4, which uses a mask having the shape that satisfies the formulas (2), (3) and in which the stannum coating layer 10 is provided on the inside surface area other than the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4, is used, has proved that the liquid leakage occurrence ratio in the environment of 45°C at 93% relative humidity is reduced greatly compared to the alkaline batteries of the comparative example 5, where the negative electrode cup 4 having the stannum coating layer 10 provided using a mask that has the shape not satisfying the formulas is used.
- the copper surface of the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is not oxidized through the film forming process, so that the creep phenomenon caused by the oxidation of the copper surface may be prevented from increasing.
- the inside surface area other than the cuff portion 4a and cuff bottom portion 4b can be provided with the stannum coating layer 10 having a higher hydrogen overpotential than copper, so that generation of hydrogen gas (H 2 ) is suppressed and as a result the liquid leakage resistance is improved.
- the mask opening shape is selected to have a tapered angle with which uniformity in coating is not damaged even if a thicker mask is used in sputtering, so that the inside surface area other than the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 having the inside surface area formed of copper can be provided with the stannum (Sn) coating layer 10 having a higher hydrogen overpotential than copper and generation of hydrogen gas (H 2 ) is suppressed.
- the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 are not coated with stannum (Sn) having a higher hydrogen potential than copper and the coating is performed with a PVD method of a dry-type film forming method, the copper surface 9 of the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is not oxidized when forming and processing a film, so that rising-up of alkaline electrolyte (creep phenomenon) is restrained from increasing and the liquid leakage resistance can be securely obtained.
- stannum (Sn) having a higher hydrogen potential than copper
- PVD method of a dry-type film forming method the copper surface 9 of the cuff portion 4a and cuff bottom portion 4b of the negative electrode cup 4 is not oxidized when forming and processing a film, so that rising-up of alkaline electrolyte (creep phenomenon) is restrained from increasing and the liquid leakage resistance can be securely obtained.
- the present invention is not limited to the above described embodiment and various other structures can be taken without departing from the gist thereof.
- the inside surface area of the negative electrode cup is coated using a thicker mask having a opening with a tapered angle by means of a PVD method of dry-type film forming method to manufacture the alkaline battery using the negative electrode cup.
- the film is favorably formed without damaging uniformity in the coating when sputtering is performed; and since only the inside surface area other than the cuff portion and cuff bottom portion made of copper of the negative electrode cup is coated with metal or metal alloy having a higher hydrogen overpotential than copper, generation of hydrogen gas (H 2 ) is restrained.
- the cuff portion and cuff bottom portion of the negative electrode cup are not coated with metal or metal alloy having a higher hydrogen potential than copper and the coating is performed with a PVD method of a dry-type film forming method, the copper surface of the cuff portion and cuff bottom portion of the negative electrode cup is not oxidized when forming and processing a film, so that only a predetermined area of the inside surface of the negative electrode cup is favorably coated with the stannum coating layer 10 and rising-up of alkaline electrolyte (creep phenomenon) is restrained from increasing.
- the position dispersion of the negative electrode cup due to deformation of the mask caused by heat on sputtering and the deformation of the mask caused when excessive coating stuck to the mask is for example removed or cleaned, are reduced, so that the coating layer, in which compared to conventional masks the dispersion in the formed state of a film is small, can be formed; and since the operating life of the mask is extended, a mask suitable for use in mass production of the negative electrode cup is obtained.
- the inside surface area of the negative electrode cup is coated by means of the PVD method of a dry-type film forming method using the mask having the shape, in which the ratio of the inside diameter of the negative electrode cup d to the diameter of the mask opening on the negative electrode cup mounting side A is 1>A/d ⁇ 0.8, so that the coated area on the inside surface of the negative electrode cup becomes larger up to around the edge of the negative electrode cup and as a result an copper exposed portion can be made smaller to further restrain the generation of hydrogen gas (H 2 ) and the preservation characteristic and liquid leakage resistance can be improved.
- H 2 hydrogen gas
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
A method for manufacturing an alkaline battery in
coin shape and button shape is provided.
In a method in which the inside surface of the
negative electrode cup 4 of an alkaline battery having a
positive active material of silver oxide or manganese
dioxide, a negative active material of zinc or zinc alloy
without containing mercury, a separator and a gasket
provided between positive electrode mixture and negative
electrode mixture, and alkaline electrolyte injected, is
coated with metal or metal alloy having a higher hydrogen
overpotential than copper, the mask 11 used for coating
processing has the shape in which: when d is the diameter
of the negative electrode cup, t is the plate thickness of
the negative electrode cup, A is the diameter of the mask
opening on the negative electrode cup mounting side, B is
the diameter of the mask opening on the negative electrode
cup supplying side, h is the depth of the negative
electrode cup, C is the thickness of mask on negative
electrode cup mounting side, and D is a tapered angle of
the mask opening on the negative electrode cup, 2(2t+d)-B>A
≧0.7d, (A/2)-h≧C>0mm, and 90°>D≧45° are satisfied to
coat only the inside surface area except a cuff portion 4a
and cuff bottom portion 4b of the negative electrode cup 4.
Description
The present invention relates to a method suitable
for use in manufacturing a coin-type or button-type
alkaline battery used in small-sized electronic equipment
such as an electronic wrist watch, an electronic desk
calculator, or the like.
Conventionally, as an alkaline battery of a coin type
or button type used in an electronic wrist watch,
electronic desk calculator, or other small-sized electronic
equipment, there has been proposed the one shown in FIG. 3.
With reference to FIG. 3, an example of a button-type
alkaline battery will be explained.
In FIG. 3, numeral 1 denotes positive electrode
mixture containing silver oxide or manganese dioxide as a
positive active material, and in this example the positive
electrode mixture 1 is formed into a pellet of a coin shape.
The positive electrode mixture of the coin-shaped pellet is
provided in a positive electrode can 2, which is composed
of a nickel-plated stainless steel plate and functions as a
positive electrode terminal and a positive electrode
current collector.
Also, numeral 3 denotes negative electrode mixture
in gel state without mercury, containing zinc or zinc alloy
powder as a negative active material and composed of
alkaline electrolyte such as sodium hydroxide aqueous
solution or potassium hydroxide aqueous solution, thickener,
and the like; and the negative electrode mixture 3 is
provided in a negative electrode cup 4 functioning as a
negative electrode terminal and a negative electrode
current collector.
Between the positive electrode mixture 1 and the
negative electrode mixture 3, a separator 5 composed of a
graft-polymerized three-layer film consisting of non woven
fabric, cellophane, and polyethylene is provided. Then, the
separator 5 is impregnated with alkaline electrolyte, for
example, sodium hydroxide aqueous solution or potassium
hydroxide aqueous solution.
A gasket 6 made of nylon is provided on the inner
periphery of the positive electrode can 2 between the upper
surface of the separator 5, and a cuff portion 4a and a
cuff bottom portion 4b of the negative electrode cup 4; and
the positive electrode can 2 is swaged and caulked to be
hermetically sealed.
As shown in FIG. 4, the negative electrode cup 4 in
this example is formed of a three-layer clad member made
of nickel (Ni) 7, stainless 8, and copper (Cu) 9; and on
the periphery thereof the cuff portion 4a and cuff bottom
portion 4b are provided. Then, the inside surface area of
copper 9 other than the cuff portion 4a and cuff bottom
portion 4b is coated with stannum (Sn) having a higher
hydrogen overpotential than copper to provide a stannum
coating layer 10.
There has been known such an example of Patent
document 1, in which only on the inside surface area of
copper 9 other than the cuff portion 4a and cuff bottom
portion 4b is coated with stannum (Sn) to provide the
stannum coating layer 10. In Patent document 1, the art
relating to a coin type and button type alkaline battery is
described in which the inside surface of the negative
electrode cup 4 other than the cuff portion 4a and cuff
bottom portion 4b thereof is coated with metal or metal
alloy having a higher hydrogen overpotential than copper by
means of a dry-type film forming method.
In the above alkaline battery, hydrogen gas (H2) can
be prevented from being generated, and since metal or metal
alloy without using mercury having a higher hydrogen
overpotential than copper is not deposited on the cuff
portion 4a and cuff bottom portion 4b of the negative
electrode cup 4, rising-up of the alkaline electrolyte
(creep phenomenon) can be prevented and liquid leakage
resistance is not deteriorated; and further since metal or
metal alloy having a higher hydrogen overpotential than
copper is deposited by means of a dry-type film forming
method, the cuff portion 4a and cuff bottom portion 4b of
the copper surface 9 are not oxidized, so that the liquid
leakage resistance can be maintained against the creep
phenomenon of the alkaline electrolyte.
Conventionally, when the inside surface area other
than the cuff portion 4a and cuff bottom portion 4b made of
copper 9 of the negative electrode cup 4 is coated with
stannum (Sn) having a higher hydrogen overpotential than
copper to provide the stannum coated layer 10, sputtering
has been used. A mask used for sputtering in Patent
document 1 is, for example, shown in FIG. 1, in which a
circular counter-boring portion of 6 mm in diameter where
the negative electrode cup 4 is mounted and fastened with a
screw and a circular opening of 5 mm in diameter provided
at the center of the counter-boring portion causing
sputtering atoms to reach the inside of the negative
electrode cup 4 are provided; and a negative electrode cup
mounting portion 21C is formed on the negative electrode
cup mounting side of the mask 21. The negative electrode
cup 4 is set such that the negative electrode cup mounting
portion 21C is covered by the negative electrode cup 4 put
from the negative electrode cup supplying side (from the
upper side in the figure), and then sputtering atoms are
projected from the negative electrode cup mounting side
(from the lower side in the figure) to be deposited. The
mask is made of comparatively thin metal plate or the like
and is shaped having the negative electrode cup mounting
portion 21C as illustrated.
A conventional mask 21 proposed in the above
mentioned Patent document 1 and used in sputtering, when
partly depositing film such that the inside surface area
other than the cuff portion 4a and cuff bottom portion 4b
of the negative electrode cup 4 is coated, has a required
opening provided in a comparatively thin metal plate or the
like to deposit a film on a predetermined portion of the
inside surface of the negative electrode cup 4. However,
the mask 21 is deformed by heat generated in sputtering or
the like to cause position dispersion with respect to the
negative electrode cup 4 mounted on the mask 21, so that
the stannum coating layer 10 can not be favorably formed on
the negative electrode cup 4, which results in
inconvenience when mass production of the negative
electrode cup 4 is conducted.
Further, such deformation generates gap between the
negative electrode cup 4 and the negative electrode cup
mounting portion 21C, so that there occurs possibility of
depositing metal or metal alloy having a higher hydrogen
overpotential than copper on the cuff bottom portion 4b or
other areas; and also there is a problem of a shorter
operating life due to the thin plate thickness of the mask,
in which such deformation as accompanied by elimination and
cleaning of an excessively-coated film adhered to the mask
21 occurs, because necessary chamber maintenance is
periodically performed for stabilizing the quality of film
in a film depositing apparatus at mass production.
In light of the above, the present invention provides
a method for manufacturing an environmentally-benign
alkaline battery without containing mercury (Hg), in which
a mask used when PVD (physical vapor deposition) method of
a dry-type film forming method is employed is appropriately
shaped and the inconvenience at mass production of the
negative electrode cup is improved.
A method for manufacturing an alkaline battery
according to the present invention is the manufacturing
method of forming and processing a coating of a negative
electrode cup by means of a PVD method such as deposition,
sputtering, ion plating, and the like, in which the coating
is performed using a mask with a mask opening in the shape
that satisfies 2(2t+d)-B≧A≧0.7d, where d is the inside
diameter of a negative electrode cup, t is the thickness of
the negative electrode cup, A is the diameter of the mask
opening on the negative electrode cup mounting side, and B
is the diameter of the mask opening on the negative
electrode cup supplying side; and that satisfies (A/2)-h≧C
>0mm, where h is the depth of the negative electrode cup,
and C is the thickness of the mask on the negative
electrode cup mounting side, with a tapered angle D of the
mask opening on the negative electrode cup mounting side
being 90°>D≧45°.
According to the method for manufacturing an alkaline
battery of the present invention, there is provided the
mask in which, for example, the diameter of the mask
opening on the negative electrode cup mounting side A is
approximately 5mm, the depth from the negative electrode
mounting surface 11d to the mask opening E is thickened
into approximately 5mm, which is conventionally 0.2mm, and
the tapered angle of the mask opening on the negative
electrode cup mounting side is made to be 45°. As described
above, since the plate is made thicker and the taper is
provided so that sputtering atoms are not blocked their
paths by the mask, coating by means of sputtering is
performed without damaging the uniformity thereof; and
since the mask is made thicker, dispersion with respect to
the position of the negative electrode cup caused by
deformation of the mask due to heat or the like on
sputtering and deformation of the mask caused when an
excessive coating adhered to the mask is removed for
cleaning is reduced, so that the operating life of the mask
becomes longer and suitable for use in the mass production.
Hereinafter, an embodiment of the method for
manufacturing an alkaline battery according to the present
invention will be described with reference to the drawings.
An example of the alkaline battery according to the
embodiment of the present invention is shown in FIG. 3. In
FIG. 3, numeral 1 denotes positive electrode mixture having
silver oxide or manganese dioxide as a positive active
material and in this example the positive electrode mixture
1 is formed into a pellet of a coin shape. The positive
electrode mixture 1 in coin shape is provided in a positive
electrode can 2 made of a stainless steel plate with nickel
plating, functioning as a positive terminal and a positive
current collector.
Further, numeral 3 denotes negative electrode mixture
in a gel state that has zinc (Zn) or zinc alloy powder as a
negative active material without containing mercury, formed
of alkaline electrolyte such as sodium hydroxide aqueous
solution or potassium hydroxide aqueous solution, thickener,
and the like; and the negative electrode mixture 3 is
provided in a negative electrode cup 4 functioning as a
negative electrode and a negative electrode current
collector.
Between the positive electrode mixture 1 and the
negative electrode mixture 3, a separator 5 composed of a
three-layer film consisting of non woven fabric, cellophane,
and polyethylene through graft polymerization is provided.
Then, the separator 5 is impregnated with alkaline
electrolyte, for example, sodium hydroxide aqueous solution
or potassium hydroxide aqueous solution.
A gasket 6 made of nylon is provided on the inside
periphery of the positive electrode can 2 between the upper
surface of the separator 5 and a cuff portion 4a and cuff
bottom portion 4b of the negative electrode cup 4; and the
positive electrode can 2 and negative electrode cup 4 are
swaged and caulked to be hermetically sealed.
In this example, as shown in FIG. 4, the negative
electrode cup 4 is formed of a three-layer clad material
made of nickel 7, stainless 8, and copper 9; and on the
periphery thereof the cuff portion 4a and cuff bottom
portion 4b are provided.
Further, the inside surface area of copper 9 other
than the cuff portion 4a and cuff bottom portion 4b is
coated by sputtering that is one of PVD methods with
stannum (Sn) having a higher hydrogen potential than
copper to provide a stannum coating layer 10.
A mask 11 hereupon used for partly forming a coating
by sputtering is shown in FIG. 2. The mask 11 has the shape
that satisfies the formula
2(2t+d)-B≧A>0.7d
, where A is the diameter of a mask opening on the
negative electrode cup mounting side, B is the diameter of
the mask opening on the negative electrode cup supplying
side, d is the inside diameter of the negative electrode
cup, and t is the thickness of the negative electrode cup.
With the dimensions described above, even if the position
of the negative electrode cup 4 is shifted on the cup
mounting surface 11d toward the side wall of the mask
opening on the mounting side of the negative electrode cup,
the cuff bottom portion 4b of the negative electrode cup 4
is not exposed to the inside of the mask opening on the
negative electrode cup mounting side, so that only the
inside surface area of the negative electrode cup 4 other
than the cuff portion 4a and cuff bottom portion 4b is
coated.
Further, the mask opening on the negative electrode
cup mounting side has the shape, in which when h is the
depth of the negative electrode cup, C is the thickness of
the mask on the negative electrode cup mounting side, and D
is a tapered angle of the mask opening on the negative
electrode cup mounting side, the formula
(A/2)-h≧C>0mm
is satisfied and the formula
90°>D≧45°
is satisfied. With the above described shape, when
sputtering atoms entering the outside portion from the
center of the negative electrode cup 4 in the oblique
direction at an angle of 45° or more is selected to be the
reference dimensions, the sputtering atoms entering in the
oblique direction are not blocked by the mask and the film
thickness on the inside wall surface is not made thin.
Accordingly, the thickness of the mask according to this
embodiment is increased to provide a mask having the
opening of dimensions suitable for the mass production.
According to the embodiment, as shown in practice
examples 1 and 2 of Table 1, since a stannum coating layer
10 having a higher hydrogen overpotential than copper is
formed on the inside surface of the negative electrode cup
4 by sputtering of a PVD method, hydrogen gas (H2) is
prevented from being generated. Further, since the cuff
bottom portion 4b of the negative electrode cup 4 is not
exposed to the inside of the mask opening on the negative
electrode cup mounting side even if the negative electrode
cup 4 is shifted on the cup mounting surface 11d when the
coating is performed, the coating layer is not formed on
the cuff portion 4a and cuff bottom portion 4b of the
negative electrode cup 4 and a copper surface of the gasket
seal portion in which rising-up of alkaline electrolyte is
less than the stannum coating layer 10 remains, and the
copper surface 9 that is a base member of the cuff portion
4a and cuff bottom portion 4b of the negative electrode cup
4 is not oxidized, so that liquid leakage resistance is
secured.
Hereupon, in a practice example 1 of Table 1 the
negative electrode cup 4 is formed as follows. First, a
three-layer clad member made of nickel 7, stainless 8, and
copper 9, having the plate thickness t=0.2mm is pressed to
form, as shown in FIG. 4, a negative electrode cup having
the inside diameter d=5.20 mm of an alkaline battery, for
example, SR626SW.
Next, the mask 11 for partly forming a film is
prepared, in which the thickness of the mask on the
negative electrode cup mounting side is 0.2mm in FIG. 2.
Then, the negative electrode cup 4 is set on the mask
11 that covers the cuff portion 4a and cuff bottom portion
4b of the negative electrode cup 4 and sputtering is
performed, so that the negative electrode cup 4 in which
the coating layer 10 of approximately 0.01 µm made of
stannum that is an example of metal having high hydrogen
overpotential is provided on the inside surface area
thereof.
Hereupon, when A is the diameter of opening of the
mask 11 and d is the inside diameter of the negative
electrode cup 4, A/d is defined as a mask opening ratio,
and in the practice example 1, sputtering is performed with
the opening ratio of mask 11 on the negative electrode cup
mounting side being 80% (opening diameter A=4.16mm) and
opening diameter of mask 11 on the cup supplying side B
being 6.20mm, that is, 2 (2t+d)-B=5.0mm>A (=4.16mm). In the
practice example 1, an alkaline battery in button shape
shown in FIG. 3 is manufactured using the above described
negative electrode cup 4.
Specifically, as shown in FIG. 3, alkaline electrolyte
consisting of sodium hydroxide aqueous solution of 28% by
weight is injected into the positive electrode can 2; then
a pellet of coin shape formed of positive electrode mixture
1 containing silver oxide, manganese dioxide, and
polyethylene tetrafluoride is inserted; and the alkaline
electrolyte is impregnated into the positive electrode
mixture.
Then, a separator 5 of a punched out circular shape
having a three-layer structure made of graft-polymerized
film formed of polyethylene and cellophane laminated and
non woven fabric is set on the pellet of the positive
electrode mixture 1; and the gasket 6 of nylon 66 coated
with nylon 610 is set.
Next, alkaline electrolyte of sodium hydroxide
aqueous solution of 28% by weight is dropped onto the non
woven fabric of the separator 5 to be impregnated. Further,
the gel-state negative electrode mixture 3 composed of zinc
alloy powder without mercury, containing aluminum (Al),
indium (In), and bismuth (Bi); thickener; and sodium
hydroxide aqueous solution is loaded; and then the negative
electrode cup 4 is mounted on the negative electrode
mixture 3.
Then, the positive electrode can 2 is swaged and
caulked to manufacture an alkaline battery, for example,
SR626SW in button shape and the alkaline battery of the
practice example 1 is thus obtained.
Further, the negative electrode cup 4 of a practice
example 2 in Table 1 is subjected to sputtering similar to
the practice example 1 except that the opening ratio of the
mask 11 on the negative electrode cup mounting side A/d is
90% (opening diameter A=4.68mm). In this case, 2(2t+d)-B=5.0mm>A(=4.68mm)
is obtained. The above negative
electrode cup 4 is used in an alkaline battery of the
practice example 2, the other structure of which is similar
to the practice example 1, to manufacture the alkaline
battery of button shape, such as SR626SW.
Further, the negative electrode cup 4 of a
comparative example 1 in Table 1 is subjected to sputtering
similar to the practice example 1 except that the opening
ratio of mask 11 on the negative electrode cup mounting
side A/d is 70% (opening diameter A=3.64mm). In this case,
2(2t+d)-B=5.0mm>A(=3.64mm) is obtained. The above negative
electrode cup 4 is used in an alkaline battery of the
comparative example 1, the other structure of which is
similar to the practice example 1, to manufacture the
alkaline battery of button shape, such as SR626SW.
Further, the negative electrode cup 4 of a
comparative example 2 in Table 1 is subjected to sputtering
similar to the practice example 1 except that the opening
ratio of mask 11 on the negative electrode cup mounting
side A/d is 100% (opening diameter A=5.20mm). In this case,
2(2t+d)-B=5.0mm<A(=5.20mm) is obtained. The above negative
electrode cup 4 is used in an alkaline battery of the
comparative example 2, the other structure of which is
similar to the practice example 1, to manufacture the
alkaline battery of button shape, such as SR626SW.
Further, the negative electrode cup 4 of a
comparative example 3 in Table 1 is subjected to sputtering
similar to the comparative example 1 except that the mask
is not used. The above negative electrode cup 4 is used in
an alkaline battery of the comparative example 3, the other
structure of which is similar to the practice example 1, to
manufacture the alkaline battery of button shape, such as
SR626SW.
One hundred alkaline batteries for each of the above
described practice examples 1, 2, and comparative examples
1 to 3 are prepared to be preserved in the environment of
45°C in temperature and at 93% relative humidity for one
hundred days; and then a liquid leakage occurrence ratio is
measured.
As a result, as shown in Table 1, each of the
alkaline batteries of the practice examples 1 and 2, where
a negative electrode cup 4, which uses a mask having the
shape that satisfies the formula (1) and in which the
stannum coating layer 10 is provided on the inside surface
area other than the cuff bottom portion 4b, is used, has
proved that the liquid leakage occurrence ratio in the
environment of 45°C in temperature and at 93% relative
humidity is lower than the alkaline batteries of
comparative examples 1 to 3, where a negative electrode
cup 4 which uses a mask having the shape that does not
satisfy the formula (1) and in which the stannum coating
layer 10 is provided.
The reason why the above results were obtained is
assumed that in alkaline batteries of the practice examples
1 and 2, if the position of the negative electrode cup 4 is
shifted on the cup mounting periphery portion 11c of the
mask 11 when the negative electrode cup 4 is coated, the
cuff portion 4a and cuff bottom portion 4b thereof are not
exposed to the inside of the opening of mask and the cuff
portion 4a and cuff bottom portion 4b of the negative
electrode cup 4 are not coated with the stannum coating
layer 10; and since the stannum coating layer 10 is coated
by means of sputtering that is a dry-type film forming
method, the cuff portion 4a and cuff bottom portion 4b of
the negative electrode cup 4 are not oxidized due to the
film formation, so that the rising-up (creep phenomenon) of
the alkaline electrolyte is prevented from increasing and
the liquid leakage resistance is improved.
Furthermore, according to the experimental results
shown in Table 1, when the mask opening ratio A/d is 80% or
90%, the liquid leakage occurrence becomes 0%; and those
results are favorable, compared to the examples in which
the ratio A/d is 70% or 100%. Accordingly, when the
relationship of 1 > A/d≧ 0. 8 is satisfied, the liquid
leakage resistance can be improved.
Moreover, according to this embodiment, as shown in a
practice example 3 of Table 2, since a taper is provided at
the opening of mask 11 on the negative electrode cup
mounting side, which satisfies the formulas (2) and (3)
where A is the diameter of mask opening on the negative
electrode cup mounting side, C is the thickness of mask on
the negative electrode cup mounting side, h is the depth of
the negative electrode cup, and D is the tapered angle of
the mask opening on the mounting side of negative electrode
cup, sputtering atoms entering the negative electrode cup 4
in the oblique direction are not blocked by the mask even
if the mask is made thicker, so that the film thickness of
the inside wall portion of the negative electrode cup 4 is
prevented from becoming thin to provide a suitable mask
used for mass production.
In Table 2, the mask used to form the coating has the
mask opening ratio of A/d=90%, and the shape of the mask
opening on the negative electrode cup mounting side is
varied to perform the coating and obtain the negative
electrode cup 4; and then, using the negative electrode
cup an alkaline battery in button shape as shown in FIG. 3
is manufactured. Specifically, in a practice example 3 of
Table 2 the negative electrode cup 4 is formed as follows.
First, a three-layer clad member made of nickel 7,
stainless 8, and copper 9, having the plate thickness
t=0.2mm is pressed and formed a negative electrode cup 4
of an alkaline battery shown in FIG. 3, for example,
SR626SW.
Next, a mask used in sputtering for partly forming a
film is provided. In the practice example 3, the mask for
partly forming a film is provided in which the depth of the
negative electrode cup is h=1.0mm, the diameter of the mask
opening on the negative electrode cup mounting side is
A=4.68mm, the thickness of the mask on the negative
electrode cup mounting side is C=1.0mm, the depth of the
mask opening from the negative electrode cup mounting
surface 11d is E=4.68mm, the tapered angle of the mask
opening on the negative electrode cup mounting side is
D=45°, and the taper is provided to cover the cuff portion
4a and cuff bottom portion 4b of the negative electrode cup
4. The mask satisfies (A/2)-h=1.34mm>C(=1.0mm).
Then, as shown in FIG. 2, the above negative
electrode cup 4 is set on the mask 11 having the taper that
covers the cuff portion 4a and cuff bottom portion 4b of
the negative electrode cup 4, in which by sputtering the
inside surface area is coated with the stannum coating
layer 10 having the thickness of 0.01µm.
In the practice example 3, the above described
negative electrode cup 4 is used, and subsequently, the
similar process to the practice example 1 in Table 1 is
used to manufacture an alkaline battery in button shape,
for example SR626SW, as shown in FIG. 3.
Further, in a comparative example 4 of Table 2, the
mask for partly forming a film is provided in which the
depth of negative electrode cup is h=1.0mm, the diameter of
the mask opening is A=4.68mm, the thickness of the mask on
the negative electrode cup mounting side and the depth of
the mask opening from the negative electrode cup mounting
surface 11d are C=E=0.20mm, and accordingly, the tapered
angle is not provided at the mask opening on the negative
electrode cup mounting side to be (A/2)-h=1.34mm>C(=0.20mm)
and cover the cuff portion 4a and cuff bottom portion 4b of
negative electrode cup 4.
The negative electrode cup 4 in the comparative
example 4 uses the above mask, and similarly to the
practice example 1 the inside surface area other than the
cuff portion 4a and cuff bottom portion 4b of the negative
electrode cup 4 is provided by sputtering the stannum
coating layer 10 of 0.01 µm in thickness.
An alkaline battery of the comparative example 4
uses the above described negative electrode cup 4, and the
other process similar to the practice example 1 is taken to
manufacture the alkaline battery in button shape, for
example, SR626SW.
Further, in a comparative example 5 of Table 2, the
mask for partly forming a film is provided in which the
depth of negative electrode cup is h=1.0mm, the diameter of
the mask opening is A=4.68mm, the thickness of the mask on
the negative electrode cup mounting side and the depth of
the mask opening from the negative electrode cup mounting
surface 11d are C=E=4.68mm, the tapered angle is not
provided at the mask opening on the negative electrode cup
mounting side to be (A/2)-h=1.34mm<C(=4.68mm) and cover the
cuff portion 4a and cuff bottom portion 4b of negative
electrode cup 4.
The negative electrode cup 4 in the comparative
example 5 uses the above mask, and similarly to the
practice example 1 the inside surface area other than the
cuff portion 4a and cuff bottom portion 4b of the negative
electrode cup 4 is coated by sputtering with the stannum
coating layer 10 of 0.01µm in thickness.
An alkaline battery of the comparative example 5
uses the above described negative electrode cup 4, and the
other process similar to the practice example 1 is taken to
manufacture the alkaline battery in button shape, for
example, SR626SW.
One hundred alkaline batteries for each of the above
described practice examples 3, and comparative examples 4,
5 are similarly to Table 1 prepared to be preserved in the
environment of 45°C in temperature and at 93% relative
humidity for one hundred days; and then the liquid leakage
occurrence ratio is measured.
As a result, as shown in Table 2, each of the
alkaline batteries of practice example 3 and comparative
example 4, where a negative electrode cup 4, which uses a
mask having the shape that satisfies the formulas (2), (3)
and in which the stannum coating layer 10 is provided on
the inside surface area other than the cuff portion 4a and
cuff bottom portion 4b of the negative electrode cup 4, is
used, has proved that the liquid leakage occurrence ratio
in the environment of 45°C at 93% relative humidity is
reduced greatly compared to the alkaline batteries of the
comparative example 5, where the negative electrode cup 4
having the stannum coating layer 10 provided using a mask
that has the shape not satisfying the formulas is used.
The reason why the above results were obtained is
assumed that since the shape of the mask satisfies the
formula (1), and further satisfies the formulas (2), (3)
with which the taper is provided, first with the shape of
mask satisfying the formula (1) the cuff bottom portion 4b
of the negative electrode cup 4 is always mounted behind
the negative electrode cup mounting periphery 11c and the
cuff portion 4a and cuff bottom portion 4b of the negative
electrode cup 4 are not coated with a film having a higher
hydrogen overpotential than copper, so that rising-up of
alkaline electrolyte (creep phenomenon) may be prevented
from increasing.
Further, since predetermined portions were coated by
sputtering of a dry-type film forming method, the copper
surface of the cuff portion 4a and cuff bottom portion 4b
of the negative electrode cup 4 is not oxidized through the
film forming process, so that the creep phenomenon caused
by the oxidation of the copper surface may be prevented
from increasing.
Furthermore, since the shape of the mask satisfies
the formulas (2) and (3), sputtering atoms entering the
negative electrode cup 4 in the oblique direction are
almost prevented from being blocked by the mask 11 despite
the fact that the mask is thick and reach the desired
inside surface area of the negative electrode cup 4, the
inside surface area other than the cuff portion 4a and cuff
bottom portion 4b can be provided with the stannum
coating layer 10 having a higher hydrogen overpotential
than copper, so that generation of hydrogen gas (H2) is
suppressed and as a result the liquid leakage resistance is
improved.
As heretofore described, according to the embodiment
of the present invention, the mask opening shape is
selected to have a tapered angle with which uniformity in
coating is not damaged even if a thicker mask is used in
sputtering, so that the inside surface area other than the
cuff portion 4a and cuff bottom portion 4b of the negative
electrode cup 4 having the inside surface area formed of
copper can be provided with the stannum (Sn) coating layer
10 having a higher hydrogen overpotential than copper and
generation of hydrogen gas (H2) is suppressed. Moreover,
since the cuff portion 4a and cuff bottom portion 4b of the
negative electrode cup 4 are not coated with stannum (Sn)
having a higher hydrogen potential than copper and the
coating is performed with a PVD method of a dry-type film
forming method, the copper surface 9 of the cuff portion 4a
and cuff bottom portion 4b of the negative electrode cup 4
is not oxidized when forming and processing a film, so that
rising-up of alkaline electrolyte (creep phenomenon) is
restrained from increasing and the liquid leakage
resistance can be securely obtained.
Furthermore, since the thicker mask is used,
deformation of the mask accompanied by formation,
maintenance of a film and the like is reduced and the
operating life of the mask is extended compared to
conventional masks, to obtain a mask suitable for mass
production of the negative electrode cup 4.
Further, needless to say, the present invention is
not limited to the above described embodiment and various
other structures can be taken without departing from the
gist thereof.
As described above, according to the method for
manufacturing an alkaline battery of the present invention,
the inside surface area of the negative electrode cup is
coated using a thicker mask having a opening with a tapered
angle by means of a PVD method of dry-type film forming
method to manufacture the alkaline battery using the
negative electrode cup. Since the thick mask having an
opening with a tapered angle not to interfere with the path
of entering sputtering atoms is used to form a film, the
film is favorably formed without damaging uniformity in the
coating when sputtering is performed; and since only the
inside surface area other than the cuff portion and cuff
bottom portion made of copper of the negative electrode cup
is coated with metal or metal alloy having a higher
hydrogen overpotential than copper, generation of hydrogen
gas (H2) is restrained. Moreover, since the cuff portion
and cuff bottom portion of the negative electrode cup are
not coated with metal or metal alloy having a higher
hydrogen potential than copper and the coating is
performed with a PVD method of a dry-type film forming
method, the copper surface of the cuff portion and cuff
bottom portion of the negative electrode cup is not
oxidized when forming and processing a film, so that only a
predetermined area of the inside surface of the negative
electrode cup is favorably coated with the stannum coating
layer 10 and rising-up of alkaline electrolyte (creep
phenomenon) is restrained from increasing. Furthermore, in
the above thick mask having the shape in which an opening
is provided with a tapered angle, the position dispersion
of the negative electrode cup due to deformation of the
mask caused by heat on sputtering and the deformation of
the mask caused when excessive coating stuck to the mask is
for example removed or cleaned, are reduced, so that the
coating layer, in which compared to conventional masks the
dispersion in the formed state of a film is small, can be
formed; and since the operating life of the mask is
extended, a mask suitable for use in mass production of the
negative electrode cup is obtained.
According to the method for manufacturing an
alkaline battery of the present invention, when the coating
is performed, the inside surface area of the negative
electrode cup is coated by means of the PVD method of a
dry-type film forming method using the mask having the
shape, in which the ratio of the inside diameter of the
negative electrode cup d to the diameter of the mask
opening on the negative electrode cup mounting side A is
1>A/d≧0.8, so that the coated area on the inside surface
of the negative electrode cup becomes larger up to around
the edge of the negative electrode cup and as a result an
copper exposed portion can be made smaller to further
restrain the generation of hydrogen gas (H2) and the
preservation characteristic and liquid leakage resistance
can be improved.
Having described preferred embodiments of the
invention with reference to the accompanying drawings, it
is to be understood that the invention is not limited to
those precise embodiments and that various changes and
modifications could be effected therein by one skilled in
the art without departing from the spirit or scope of the
invention as defined in the appended claims.
Claims (6)
- A method for manufacturing an alkaline battery in which silver oxide or manganese dioxide is a positive active material, zinc or zinc alloy powder without containing mercury is a negative active material, a separator and a gasket are provided between positive electrode mixture and negative electrode mixture, the inside surface of a negative electrode cup having alkaline electrolyte injected is coated with metal or metal alloy having a higher hydrogen overpotential than copper, and said coating process is performed by means of a PVD method such as deposition, sputtering, ion plating or the like, wherein
said coating is provided using a mask having the shape that satisfies: - A method for manufacturing an alkaline battery according to claim 1, wherein
said mask has the shape that satisfies
(A/2)-h ≧ C > 0 mm, where h is the depth of said negative electrode cup and C is the thickness of the mask on the negative electrode cup mounting side. - A method for manufacturing an alkaline battery according to claim 1, wherein
said coating is provided using the mask having the mask opening with a tapered angle on the negative electrode cup mounting side D that satisfies 90°>D≧45°. - A method for manufacturing an alkaline battery according to claim 1, wherein
said coating is provided using the mask having the shape in which a ratio of the inside diameter of the negative electrode cup d to the diameter of the mask opening on the negative electrode cup mounting side A satisfies 1>A/d≧0.8. - A method for manufacturing an alkaline battery according to claim 1, wherein
said negative electrode cup is formed of a three-layer clad member of nickel, stainless and copper, and has a cuff portion and a cuff bottom portion formed on the outer periphery thereof. - A method for manufacturing an alkaline battery according to claim 1, wherein
said coating is provided with stannum (Sn) having a higher hydrogen overpotential than copper (Cu) to form a stannum coating layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003129637A JP3901122B2 (en) | 2003-05-07 | 2003-05-07 | Manufacturing method for negative electrode cup of alkaline battery |
| JP2003129637 | 2003-05-07 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1505668A2 true EP1505668A2 (en) | 2005-02-09 |
| EP1505668A3 EP1505668A3 (en) | 2007-11-28 |
| EP1505668B1 EP1505668B1 (en) | 2009-03-11 |
Family
ID=33410535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04010472A Expired - Lifetime EP1505668B1 (en) | 2003-05-07 | 2004-05-03 | Method for manufacturing alkaline battery |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7314492B2 (en) |
| EP (1) | EP1505668B1 (en) |
| JP (1) | JP3901122B2 (en) |
| CN (1) | CN1276533C (en) |
| DE (1) | DE602004019853D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3742514A1 (en) * | 2019-05-20 | 2020-11-25 | VARTA Microbattery GmbH | Method for producing a battery and battery produced according to the method |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4347759B2 (en) * | 2004-07-07 | 2009-10-21 | Ｔｄｋ株式会社 | Electrode manufacturing method |
| JP4851707B2 (en) * | 2004-12-15 | 2012-01-11 | セイコーインスツル株式会社 | Method for producing alkaline battery |
| ATE486379T1 (en) * | 2005-04-29 | 2010-11-15 | Eveready Battery Inc | ANODE HOUSING FOR AN ALKALINE CELL |
| US7993508B2 (en) * | 2006-11-01 | 2011-08-09 | Eveready Battery Company, Inc. | Method of forming an electrode casing for an alkaline electrochemical cell with reduced gassing |
| US20080226976A1 (en) | 2006-11-01 | 2008-09-18 | Eveready Battery Company, Inc. | Alkaline Electrochemical Cell with Reduced Gassing |
| FR2958796B1 (en) * | 2010-04-13 | 2012-04-13 | Rhodia Operations | POLYAMIDE SEAL TRIM FOR ALKALINE BATTERIES. |
| DE102011078611B4 (en) * | 2011-07-04 | 2015-02-05 | Varta Microbattery Gmbh | High internal volume button cell and method of making this button cell |
| GB2493525A (en) * | 2011-08-06 | 2013-02-13 | Ceram Res Ltd | Applying coating material to part of an article |
| US9548511B2 (en) | 2012-07-18 | 2017-01-17 | Nthdegree Technologies Worldwide Inc. | Diatomaceous energy storage devices |
| US10396365B2 (en) | 2012-07-18 | 2019-08-27 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| TWI680883B (en) | 2012-07-18 | 2020-01-01 | 澳大利亞商印製能源技術有限公司 | Energy storage devices and ink for printed film |
| US9520598B2 (en) | 2012-10-10 | 2016-12-13 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
| US9397341B2 (en) | 2012-10-10 | 2016-07-19 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
| WO2015009867A1 (en) * | 2013-07-17 | 2015-01-22 | Nthdegree Technologies Worldwide Inc. | Printed silver oxide batteries |
| EP3745490B1 (en) * | 2019-05-28 | 2024-03-20 | VARTA Microbattery GmbH | Method for producing a battery and battery produced according to the method |
| WO2022010249A1 (en) * | 2020-07-10 | 2022-01-13 | 삼성에스디아이 주식회사 | Rechargeable battery |
| CN115295934B (en) * | 2022-08-08 | 2024-04-26 | 常州长盈精密技术有限公司 | Cylindrical battery shell, cylindrical battery and manufacturing process of cylindrical battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2220108A (en) * | 1988-06-22 | 1989-12-28 | Avx Corp | Method of depositing conductive paths on a substrate |
| JPH04236758A (en) * | 1991-01-16 | 1992-08-25 | Oki Electric Ind Co Ltd | Mask for vapor deposition |
| EP1187236A2 (en) * | 2000-09-08 | 2002-03-13 | Sony Corporation | Alkaline battery |
| US6402796B1 (en) * | 2000-08-07 | 2002-06-11 | Excellatron Solid State, Llc | Method of producing a thin film battery |
| US20020111035A1 (en) * | 2001-01-26 | 2002-08-15 | Seiko Epson Corporation | System and methods for manufacturing and using a mask |
| US6558836B1 (en) * | 2001-02-08 | 2003-05-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Structure of thin-film lithium microbatteries |
-
2003
- 2003-05-07 JP JP2003129637A patent/JP3901122B2/en not_active Expired - Lifetime
-
2004
- 2004-04-29 US US10/834,673 patent/US7314492B2/en active Active
- 2004-05-03 EP EP04010472A patent/EP1505668B1/en not_active Expired - Lifetime
- 2004-05-03 DE DE602004019853T patent/DE602004019853D1/en not_active Expired - Lifetime
- 2004-05-07 CN CNB2004100477144A patent/CN1276533C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2220108A (en) * | 1988-06-22 | 1989-12-28 | Avx Corp | Method of depositing conductive paths on a substrate |
| JPH04236758A (en) * | 1991-01-16 | 1992-08-25 | Oki Electric Ind Co Ltd | Mask for vapor deposition |
| US6402796B1 (en) * | 2000-08-07 | 2002-06-11 | Excellatron Solid State, Llc | Method of producing a thin film battery |
| EP1187236A2 (en) * | 2000-09-08 | 2002-03-13 | Sony Corporation | Alkaline battery |
| US20020111035A1 (en) * | 2001-01-26 | 2002-08-15 | Seiko Epson Corporation | System and methods for manufacturing and using a mask |
| US6558836B1 (en) * | 2001-02-08 | 2003-05-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Structure of thin-film lithium microbatteries |
Non-Patent Citations (1)
| Title |
|---|
| THIN SOLID FILMS, vol. 398-399, 2001, pages 572-574, XP002454794 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3742514A1 (en) * | 2019-05-20 | 2020-11-25 | VARTA Microbattery GmbH | Method for producing a battery and battery produced according to the method |
| US11258145B2 (en) | 2019-05-20 | 2022-02-22 | Varta Microbattery Gmbh | Battery and process for producing a battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3901122B2 (en) | 2007-04-04 |
| US7314492B2 (en) | 2008-01-01 |
| EP1505668B1 (en) | 2009-03-11 |
| EP1505668A3 (en) | 2007-11-28 |
| CN1276533C (en) | 2006-09-20 |
| CN1551390A (en) | 2004-12-01 |
| DE602004019853D1 (en) | 2009-04-23 |
| US20040221446A1 (en) | 2004-11-11 |
| JP2004335265A (en) | 2004-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1505668A2 (en) | Method for manufacturing alkaline battery | |
| US6830847B2 (en) | Zinc/air cell | |
| JP3060145B2 (en) | Mercury-free miniature zinc-air battery with indium-plated anode cup | |
| EP1187236B1 (en) | Alkaline battery | |
| CN1797811B (en) | Negative electrode can, alkaline cell and production method for same | |
| EP1875530B1 (en) | Alkaline cell anode casing | |
| CA2421498A1 (en) | Electrode for rechargeable lithium battery and rechargeable lithium battery | |
| WO2006057788A1 (en) | Zinc/air cell | |
| EP2101367A1 (en) | Method for producing alkaline battery, and alkaline battery | |
| JP2007080614A (en) | Alkaline battery | |
| JP2006228503A (en) | Alkaline battery | |
| US20060127757A1 (en) | Alkaline cell and production method for same | |
| JP3522303B2 (en) | Button type alkaline battery | |
| JP2004031321A (en) | Galvanic cell | |
| JP3997804B2 (en) | Alkaline battery | |
| JP4717222B2 (en) | Alkaline battery | |
| US20130230763A1 (en) | Housing for mercury-free button cells | |
| JP2004530282A (en) | Anode can for electrochemical cell | |
| JP4166431B2 (en) | Alkaline battery | |
| JPH09147816A (en) | Alkaline button battery | |
| JP2003223898A (en) | Nonaqueous electrolytic battery | |
| JP2008123839A (en) | Manufacturing method of alkaline battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01M 4/62 20060101ALI20071018BHEP Ipc: H01M 6/08 20060101ALI20071018BHEP Ipc: H01M 2/02 20060101AFI20041215BHEP Ipc: C23C 14/04 20060101ALI20071018BHEP Ipc: H01M 10/28 20060101ALI20071018BHEP |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK |
|
| 17P | Request for examination filed |
Effective date: 20080423 |
|
| AKX | Designation fees paid |
Designated state(s): CH DE FR GB LI |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB LI |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: ISLER & PEDRAZZINI AG Ref country code: CH Ref legal event code: EP |
|
| REF | Corresponds to: |
Ref document number: 602004019853 Country of ref document: DE Date of ref document: 20090423 Kind code of ref document: P |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20091214 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 746 Effective date: 20120702 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R084 Ref document number: 602004019853 Country of ref document: DE Effective date: 20120614 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20140521 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20140527 Year of fee payment: 11 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150503 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150503 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150601 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: MURATA MANUFACTURING CO., LTD., JP Free format text: FORMER OWNER: TOHOKU MURATA MANUFACTURING CO., LTD, JP Ref country code: CH Ref legal event code: PUE Owner name: TOHOKU MURATA MANUFACTURING CO., LTD, JP Free format text: FORMER OWNER: SONY CORPORATION, JP |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602004019853 Country of ref document: DE Ref country code: DE Ref legal event code: R081 Ref document number: 602004019853 Country of ref document: DE Owner name: MURATA MANUFACTURING CO., LTD., NAGAOKAKYO-SHI, JP Free format text: FORMER OWNER: TOHOKU MURATA MANUFACTURING CO., LTD, KORIYAMA-SHI, JP Ref country code: DE Ref legal event code: R081 Ref document number: 602004019853 Country of ref document: DE Owner name: MURATA MANUFACTURING CO., LTD., NAGAOKAKYO-SHI, JP Free format text: FORMER OWNER: SONY CORPORATION, TOKIO/TOKYO, JP |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602004019853 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: H01M0002020000 Ipc: H01M0050100000 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230519 Year of fee payment: 20 Ref country code: CH Payment date: 20230605 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 602004019853 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |